Insertion of alkynes into Ni-H bonds: Synthesis of novel vinyl nickel(II) and dinuclear vinyl nickel(II) complexes containing a [P, S]-ligand

Article abstract of DOI:10.1021/om0606340

Reactions of alkynes with nickel hydride complexes bearing a [P, S]-ligand and supported by trimethylphosphine were investigated. Tetracoordinate vinyl nickel(II) complexes 3, 5, and 6 with square-monoinsertionplanar geometry were obtained by reacting phenylacetylene, trimethylsilylacetylene, and 1-hexyne with the hydrido nickel complex 1. Reaction of 1,4-bis(trimethylsilylethynyl)benzene with complex 1 proceeds as a monoinsertion and afforded complex 7, while reaction of 1,4-bis(ethynyl)benzene with 1 leads to the dinuclear vinyl nickel(II) complex 8.

Full text of DOI:10.1021/om0606340

566
Organometallics 2007, 26, 566-570
Insertion of Alkynes into Ni-H Bonds: Synthesis of Novel Vinyl
Nickel(II) and Dinuclear Vinyl Nickel(II) Complexes Containing a
[P, S]-Ligand
Lei She,† Xiaoyan Li,*,† Hongjian Sun,† Jun Ding,† Markus Frey,‡ and
Hans-Friedrich Klein‡
School of Chemistry and Chemical Engineering, Shandong UniVersity, Shanda Nanlu 27, 250100 Jinan,
People’s Republic of China, and Fachbereich Chemie, Technische UniVersita¨t Darmstadt,
Petersenstrasse 18, 64287 Darmstadt, Germany
ReceiVed July 14, 2006
Reactions of alkynes with nickel hydride complexes bearing a [P, S]-ligand and supported by
trimethylphosphine were investigated. Tetracoordinate vinyl nickel(II) complexes 3, 5, and 6 with square-
planar geometry were obtained by reacting phenylacetylene, trimethylsilylacetylene, and 1-hexyne with
the hydrido nickel complex 1. Reaction of 1,4-bis(trimethylsilylethynyl)benzene with complex 1 proceeds
as a monoinsertion and afforded complex 7, while reaction of 1,4-bis(ethynyl)benzene with 1 leads to
the dinuclear vinyl nickel(II) complex 8.
Scheme 1
Introduction
Oligomerization and polymerization of alkynes may occur
by two different routes: (a) alkyne insertion yielding vinyl
complexes; (b) alkyne metathesis via transition-metal carbene
complexes. The first pathway is probably more common and is
illustrated in a general sense in Scheme 1. In this insertion
process the σ-vinyl metal complexes are important intermediates,
through which the carbon chain is propagated.1 However, in
most cases the vinyl complexes have not been isolated from
the reaction system.
In the commercially significant Shell Higher Olefin Process
(SHOP)2 hydrido nickel(II) complexes containing [P, O]-chelate
ligands are considered as the active species.3 Therefore studies
on the reactivity of [Ni-H] units are of great importance. Some
reports on 2-(diphenylphosphino)thiophenole as a chelating
ligand have been published. Most of these studies are concerned
with bis- and tris-chelate complexes of 3d, 4d, and 5d metals.4-7
There are few examples of stable mono[P, S]-chelate complexes
of 4d and 5d elements.8,9
and its insertion reactions with different alkynes. The studied
alkynes include phenylacetylene, trimethylsilylacetylene, 1-hex-
yne, 1,4-bis(ethynyl)benzene, and 1,4-bis(trimethylsilylethynyl)-
benzene.
Results and Discussion
1. Synthesis of Hydrido Nickel Complex 1. The reaction
of Ni(PMe3)4 or Ni(PMe3)2(COD) with 1 molar equiv of
2-(diphenylphosphino)thiophenol in the presence of excess (5
times) trimethylphosphine gave rise to hydrido(2-diphenylphos-
phinyl)thiophenolatobis(trimethylphosphine)nickel(II) (1) (eq 1).
In this paper, we report the synthesis of hydrido(2-diphen-
ylphosphinyl)thiophenolatobis(trimethylphosphine)nickel(II) (1)
* To whom correspondence should be addressed. Fax: +86-531-
88564464. E-mail: xli63@sdu.edu.cn.
† Shandong University.
‡ Technische Universita¨t Darmstadt.
(1) (a) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G.
Principles and Applications of Organotransition Metal Chemistry; Univer-
sity Science Books: New York, 1987; p 577. (b) Chaulagain, M. R.;
Mahandru, G. M.; Montgomery, J. Tetrahedron 2006, 62, 7560-7566.
(2) Keim, W; Behr, A.; Schmitt, G. Technische Produkte und Prozesse,
1; Aufl. Verlag Salle Sauerlaender, Ffm, 1986.
(3) Peuckert, M.; Keim, W. Organometallics 1983, 2, 594-601.
(4) Block, E.; Ofori-Okai, G.; Kang, H.; Zubieta, J. Inorg. Chim. Acta
1991, 188, 7-13.
Crystallization at -27 °C afforded a red crystalline solid in
30-40% yield. Complex 1 in the solid state is stable below 65
°C and quickly decomposes at room temperature in solution.
(5) Dilworth, J. R.; Lu, C.; Miller, J. R.; Zheng, Y. J. Chem. Soc., Dalton
Trans. 1995, 1957-1964.
In the IR spectrum the (Ni-H) band was found at 1907 cm-1
.
(6) Kim, J. S.; Reibenspies, J. H.; Darensbourg, M. Y. Inorg. Chim. Acta
1996, 250, 283-294.
The resonance of the hydrido hydrogen in the 1H NMR spectrum
at room temperature is registered at -19.9 ppm as a doublet
(7) Perez-Lourido, P.; Romero, J.; Garcia-Vazquez, J. A.; Sousa, A.;
Zubieta, J.; Maresca, K. Polyhedron 1998, 17, 4457-4464.
(8) Dahlenburg, L.; Herbst, K.; Kuehnlein, M. Z. Anorg. Allg. Chem.
1997, 623, 250-258.
2
with the coupling constant J(P, H) ) 41 Hz. At 203 K the
ligand exchange is decelerated so as to split up the one doublet
2
of triplets with the coupling constant J(Pphenyl, H) ) 45 Hz
(9) Dilworth, L. R.; Morales, D.; Zheng, Y. J. Chem. Soc., Dalton Trans.
1984, 459-467.
2
and J(Pmethyl, H) ) 9 Hz. This multiplicity accords with a
10.1021/om0606340 CCC: $37.00 © 2007 American Chemical Society
Publication on Web 12/24/2006

Insertion of Alkynes into Ni-H Bonds
Organometallics, Vol. 26, No. 3, 2007 567
trigonal bipyramidal coordination geometry. In the 31P NMR
spectrum this conjecture is proved through a double doublet
for the chelating phosphorus atom at 57.5 ppm with a coupling
2
constant J(P, P) ) 9 Hz and a double doublet for the two
trimethylphosphine phosphorus atoms at -14.4 ppm with the
same coupling constants.
Complex 1 in solution is very unstable and decomposes to
bis-chelated complex 2 within several minutes (eq 2). The
decomposition mechanism is proposed.10 Therefore in this paper
all of the reactions with complex 1 were carried out without
isolation of complex 1.
2. Reaction with Phenylacetylene. Hydrido nickel complex
1, which is in situ generated in THF through the reaction of
Ni(PMe3)4 with 2-(diphenylphosphino)thiophenole, in the pres-
ence of phenylacetylene afforded tetracoordinate vinyl nickel-
(II) complexes 3 (eq 3). Complex 3 was fully characterized by
Figure 1. Molecular structure of 3 and selected bond distances
(Å) and angles (deg): Ni1-C20 1.918(6), Ni1-P1 2.1618(17),
Ni1-P2 2.181(2), Ni1-S1 2.1994(18), S1-C18 1.755(6), P1-C13
1.812(5), C19-C20 1.329(8); C20-Ni1-P1 90.54(19), C20-Ni1-
P2 89.26(19), P1-Ni1-P2 174.72(8), C20-Ni1-S1 177.5(2), P1-
Ni1-S1 89.59(6), P2-Ni1-S1 90.84(7), C18-S1-Ni1 106.56(19),
C13-P1-C12 105.6(2), C13-P1-C1 104.2(3), C12-P1-C1
106.4(3), C13-P1-Ni1 108.25(19), C12-P1-Ni1 115.51(19),
C1-P1-Ni1 115.8(2).
equilibrium between tetracoordinate complex 3 and pentacoor-
dinate complex 4 at low temperature (eq 4). Our efforts to isolate
complex 4 were not successful.
IR and NMR spectroscopy. In the IR spectra the typical (Ni-
H) absorption at 1907 cm-1 of the hydrido nickel complex 1 is
absent. The H NMR spectrum (in CDCl3) revealed two vinyl
1
protons at 4.7 and 5.79 ppm as singlets, respectively, indicating
that Markovnikov addition of the Ni-H bond to phenylethyne
has occurred.11 In the 31P NMR spectrum doublets at -12.8
and 51.2 ppm are assigned to the trimethylphosphine ligand and
to the diphenylphosphanyl group, respectively. The large
coupling constant (2J(PP) ) 280 Hz) implies a trans-orientation
of these two P nuclei in solution. The molecular structure of
complex 3 was confirmed for the crystal by an X-ray diffraction
analysis.
The molecular structure of complex 3 is shown in Figure 1.
The nickel atom displays a square-planar geometry with two
P-donor atoms lying in trans-positions. The vinyl group is
oriented perpendicular to the coordination plane, and the Ni1-
C20 bond length of 1.918(6) Å is almost the same as that the
Ni-Cvinyl bond (1.916 Å) in trans-[Ni(C6Cl5)(PMe3)2{C(OMe)d
CH2}]12 and falls in the typical range for σ-vinyl complexes of
cobalt(III).13
3. Reaction with Trimethylsilylacetylene. When trimeth-
ylsilylethyne is used instead of phenylethyne, an analogous four-
coordinate vinyl nickel(II) complex, 5, is directly obtained from
ether solution as orange rhombic crystals (eq 5). At room
temperature complex 5 is stable in the air for several hours.
The reaction (eq 3) is better carried out in a polar medium
(THF), giving less byproduct 2 than in pentane. Complex 3 is
stable at room temperature. If 1 equiv of trimethylphosphine is
added to a solution of complex 3, the color below - 80 °C
changes from yellow to red; otherwise the solution remains
yellow. According to our early observation about the equilibrium
between a pentacoordinate vinyl cobalt(III) complex and a
hexacoordinate vinyl cobalt(III) complex,13 we suggest an
1
In the H NMR spectrum (in C6D6), the two vinyl protons
(10) Frey, M. Doctoral Thesis, Technische Universitaet Darmstadt,
Germany, 2005.
appear as singlets at 5.78 and 6.13 ppm, respectively. When
compared with the vinyl protons in complex 3, the signals are
shifted downfield by the electron-donating trimethylsilyl group.
Two 31P NMR doublets at -14.2 and 46.8 ppm with 2J(PP) )
280 Hz indicate a trans-arrangement of the two phosphorus
nuclei.
(11) Kuramoto, A.; Nakanishi, K.; Kawabata, T.; Komine, N.; Hirano,
M.; Komiya, S. Organometallics 2006, 25, 311.
(12) Xu, D.; Miki, K.; Tanaka, M.; Kasai, N.; Yasuoka, N.; Wada, M.
J. Organomet. Chem. 1989, 371, 267-277.
(13) Klein, H.-F.; Li, X.; Floerke, U.; Haupt, H-J. Z. Naturforsch. 2000,
55b, 707-717.

568 Organometallics, Vol. 26, No. 3, 2007
She et al.
spectrum is almost as large as that for complexes 3 and 5 (2J(PP)
) 280 Hz), indicating a trans-orientation of the two phosphorus
atoms.
5. Reaction with 1,4-Bis(trimethylsilylethynyl)benzene.
When 1,4-bis(trimethylsilylethynyl)benzene was added to tet-
rakis(trimethylphosphine)nickel(0) and 2-diphenylphosphi-
nothiophenole in diethyl ether, the dark red solution rapidly
turned yellow-brown. Complex 7 was isolated as a 4:1 ((Z)-7:
(E)-7) mixture of isomers from diethyl ether at -20 °C as a
yellow powder in 76% yield (eq 7).
Figure 2. Molecular structure of 5 and selected distances (Å) and
angles (deg): S1-Ni1 2.2117(9), Ni1-C22 1.911(3), Ni1-P2
2.1546(8), Ni1-P1 2.1819(9), S1-C11 1.769(3), P2-C10 1.815-
(3), C22-C23 1.336(4); C11-S1-Ni1 105.47(9), C22-Ni1-P2
90.06(8), C22-Ni1-P1 93.51(9), P2-Ni1-P1 155.77(3), C22-
Ni1-S1 168.86(9), P2-Ni1-S1 90.10(4), P1-Ni1-S1 90.90(4).
A strong infrared absorption at 2152 cm-1 indicates the
presence of a CtC bond. In the H NMR spectrum, the two
1
An X-ray diffraction study reveals that complex 5 attains a
molecular structure (Figure 2) that is closely related with
complex 3. The bulky trimethylsilyl group renders the angle
P2-Ni1-P1 (155.77(3)°) significantly smaller than that in
complex 3 (174.72(8)°).
It is known that ligands containing a C(sp2)-Si bond can be
very sensitive to water.13,14 Hydrolysis is expected to give rise
to a C(sp2)-H bond along with Me3SiOH and/or (Me3Si)2O as
byproducts. However, IR and 1H NMR spectroscopic data
confirmed that there was no reaction in THF/water solution of
complex 5. Hydrolysis appears to require special conditions,
and the mechanism is not fully understood.15
trimethylsilyl groups appear as singlets at 0.22 and -0.15 ppm,
indicating different chemical surroundings after a monoinsertion
reaction. A signal for the vinyl protons is observed as a singlet
at 6.78 ppm. The 13C NMR data clearly show resonances of
both CdC bonds (141.7 and 157.1 ppm) and CtC bonds (93.6
and 105.7 ppm).
In the 31P NMR spectrum four doublet signals were found,
which can be divided into two groups for the two isomers. Each
group consists of a doublet for the trimethylphosphine ligand
and a doublet for the diphenylphosphino group. The observed
multipicity is consistent with the presence of Z and E isomers
of complex 7 in solution. The larger coupling constant [J(PMe3-
PPh2) ) 345 Hz] is assigned to (E)-7. The bulky trimethylsilyl
group appears to favor a trans-orientation with respect to the
nickel center as a result of repulsion with the diphenylphosphino
group of the chelate ligand. These effects cause a smaller angle
P-Ni-P in (Z)-7 and consequently a smaller coupling constant
[J(PMe3-PPh2) ) 280 Hz] in (Z)-7. The ratio of (Z)-7 and (E)-7
in CDCl3 at 295 K is 4:1.
4. Reaction with 1-Hexyne. Insertions of phenylethyne and
trimethylsilylethyne into the Ni-H bond preferentially gave
branched vinyl nickel complexes. In order to better understand
In order to generate a dinuclear nickel vinyl compound,
complex 7 was added to a solution of tetrakis(trimethylphos-
phine)nickel(0) and 2-(diphenylphosphino)thiophenole. Spec-
troscopic examination of the reaction mixture verified the
generation of a nickel hydride. However, the expected double
insertion reaction did not occur, presumably because the bulky
trimethylsilyl group prevents an insertion reaction of the second
(CtC) group. Similar results have been reported before.16
6. Reaction with 1,4-Bis(ethynyl)benzene. Addition of 1,4-
bis(ethynyl)benzene to a solution of Ni(PMe3)4 and 2-(diphen-
ylphosphino)thiophenole in THF afforded a yellow-brown
solution. Complex 8 was obtained from pentane at -20 °C as
yellow-brown microcrystals. In the IR spectrum the absence of
a (CtC) band around 2100 cm-1 indicates the formation of
the dinickel complex 8 (eq 8). The NMR data are consistent
the regioselectivity of the insertion reaction and the influence
of both steric and electron effects upon the reaction products,
1-hexyne was introduced. In this case a branched vinyl nickel
complex 6 was also obtained. The 1H NMR spectrum (in CDCl3)
of complex 6 reveals two vinyl protons at 4.50 and 5.07 ppm
as singlets, which were coincident with that of complexes 3
and 5. The coupling constant (2J(PP) ) 278 Hz) in the 31P NMR
(14) (a) Bianchini, C.; Marchi, A.; Marvelli, L.; Peruzzini, M.; Romerosa,
A.; Rossi, R. Organometallics 1996, 15, 3804. (b) Barbaro, P.; Bianchini,
C.; Peruzzini, M.; Polo, A.; Zanobini, F. Inorg. Chim. Acta 1994, 220, 5.
(c) Rappert, T.; Nurnberg, O.; Werner, H. Organometallics 1993, 12, 1359.
(d) Li, X. Doctoral Thesis, Technische Universitaet Darmstadt: Germany,
1999.
1
with two square-planar nickel units in complex 8. In the H
NMR spectrum four vinyl protons appear as two singlets at 5.11
(2 H) and 6.03 ppm (2 H). The 13C NMR and 31P NMR spectra
(15) Wen, T. B.; Zhou, Z. Y.; Jia, G. Angew. Chem., Int. Ed. 2001, 40,
1591.
(16) Xia, H. P.; Yeung, R. C. Y.; Jia, G. Organometallics 1998, 17, 4762.

Insertion of Alkynes into Ni-H Bonds
Organometallics, Vol. 26, No. 3, 2007 569
was filtrated. Crystallization of the filtrate at -27 °C afforded
hydrido nickel(II) complex 1 as light red, small, thin plates. Yield:
0.67 g of 1 (37.0%), mp (dec) > 65 °C. Anal. Calcd for C24H33-
NiP3S (505.20 g/mol): C, 57.06; H, 6.58; P, 18.39. Found: C,
57.80; H, 6.95; P, 17.91. IR (Nujol): ν ) 1907 (Ni-H) cm-1. 1H
NMR (300 MHz, d8-THF, 203 K, ppm): δ (CH), 7.71-7.64 (m,
4H); δ (CH), 7.44-7.32 (m, 7H), δ (CH), 7.09 (m, 2H), δ (CH),
6.86 (m, 1H), δ (PCH3), 1.15 (s, 18H), δ (NiH) -19.9 (dt, 2J(PH)
clearly confirm the dinuclear nature of the vinyl nickel(II)
complex 8. The quality of single crystals was not sufficient for
an X-ray analysis.
2
) 45 Hz, J(PH) ) 9 Hz, 1H). 31P NMR (81 MHz, d8-THF, 203
2
K, ppm): δ (PPh2), 57.5 (dd, 2J(PphPme) ) 154 Hz, J(PphPme)
) 18 Hz, 1P); δ (PMe3), -14.4 (dd, 2J(PmePph) ) 154 Hz,
2J(PmePph) ) 18 Hz, 2P).
[(1-Phenylethenyl)[(2-diphenylphosphino)thiophenyl(S,P)]-
trimethylphosphine]nickel(II) (3). Tetrakis(trimethylphosphine)-
nickel(0) (2.36 g, 6.40 mmol) was dissolved in 40 mL of THF. To
this solution was added 2-(diphenylphosphino)benzenethiole (1.93
g, 6.56 mmol) in 20 mL of THF at -80 °C. The mixture was stirred
and turned dark red when warmed to 20 °C. Phenylethyne (2.75 g,
26.96 mmol) was injected into the mixture, which rapidly turned
brown. After 18 h, the color changed to yellow-brown. Filtration
and evaporation of the filtrate in vacuo followed by washing with
pentane resulted in a yellow powder, which was crystallized from
diethyl ether at -27 °C. Complex 3 formed yellow cubic crystals
suitable for X-ray diffraction analysis. Yield: 1.40 g of 3 (47.0%),
mp (dec) > 135 °C. Anal. Calcd for C29H30NiP2S (531.24 g/mol):
C, 65.57; H, 5.70. Found: C, 65.60; H, 5.95. IR (Nujol): ν ) 1587,
Conclusion
In situ reactions of alkynes with a nickel hydride complex
bearing a [P, S]-ligand and supported with trimethylphosphine
were investigated. Tetracoordinate vinyl nickel(II) complexes
3, 5, and 6 with square-planar geometry were obtained through
formal insertion reactions of phenylacetylene, trimethylsilyl-
acetylene, and 1-hexyne with an intermediate hydrido nickel
complex, 1. The reaction of 1,4-bis(trimethylsilylethynyl)-
benzene afforded the monoinsertion complex 7, while the
reaction of 1,4-bis(ethynyl)benzene leads to the dinuclear vinyl
nickel(II) complex 8. This reaction will open up access to
bimetallic, oligomeric, or polymeric organonickel compounds
with conjugated bridges, which have interesting potential as
molecular conductors.17
1
1570, 1549 (CdC) cm-1. H NMR (300 MHz, CDCl3, 294 K,
2
ppm): δ [P (CH3)3], 1.29 (d, J(PH) ) 9 Hz, 9H); δ (Ni-C-
CH2), 4.74 (s, 1H), 5.79 (s, 1H); δ (CHarom), 6.77-7.97 (m, 19H).
13C NMR (75 MHz, CDCl3, 297 K, ppm): δ (PCH3), 14.15 (d,
1J(PC) ) 27.7 Hz); δ (Ni-C-CH2),117.3; δ (Ni-C-CH2), 163.1 (t,
Investigation of the catalytic properties of complexes 3, 5,
and 6 is in progress.
1
| J(PC) + 3J(PC)| ) 59 Hz); δ (C-S), 157; δ (CH2-C-C), 145.2; δ
(Carom), 121.9, 125.3, 126.9, 127.4, 128.3, 129.3, 130.2, 130.8,
132.0, 132.9, 133.4. 31P NMR (121 MHz, CDCl3, 295 K, ppm): δ
(PCH3), -12.8 (d, 2J(PP) ) 280 Hz, 1P); δ (PPh2), 51.2 (d, 2J(PP)
) 280 Hz, 1P).
Experimental Section
General Procedures and Materials. Standard vacuum tech-
niques were used in manipulations of volatile and air-sensitive
materials. Tetrakis(trimethylphosphine)nickel(0),18 2-(diphenylphos-
phino)benzenethiol,19 phenylethyne,20 trimethylsilylethyne,21 1,4-
bis(timethylsilylethynyl)benzene,22 and 1,4-bis(ethynyl)benzene23
were synthesized according to literature procedures. Infrared spectra
(4000-400 cm-1), as obtained from Nujol mulls between KBr
[(1-(Trimethylsilyl)ethenyl)[(2-diphenylphosphino)thiophenyl-
(S,P)]trimethylphosphan]nickel(II) (5). Adding a solution of
2-(diphenylphosphino)benzenethiol (1.27 g, 4.32 mmol) in 20 mL
of THF to a solution of tetrakis(trimethylphosphine)nickel(0) (1.57
g, 4.32 mmol) in 40 mL of THF at -80 °C afforded a dark red
solution. Trimethylsilylethyne (0.80 g, 8.16 mmol) was injected
into the mixture, and a dark red suspension formed rapidly. After
stirring for 18 h at room temperature, a brown suspension was
obtained. The filtrate was evaporated in vacuo, and the residue was
extracted with pentane/diethyl ether (1:1). Crystallization in diethyl
ether at -27 °C afforded complex 5 as orange rhombus crystals
suitable for X-ray diffraction analysis. Yield: 1.16 g (51.0%), mp
(dec) > 122 °C. Anal. Calcd for C26H34NiP2SSi (527.33 g/mol):
C, 59.22; H, 6.50. Found: C, 59.48; H, 6.85. IR (Nujol): ν ) 1571,
disks, were recorded on a Nicolet 5700. H, 13C, and 31P NMR
1
(300, 75, and 121 MHz, respectively) spectra were recorded on a
Bruker Avance 300 spectrometer. 13C and 31P NMR resonances
were obtained with broadband proton decoupling. Elemental
analyses were carried out on an Elementar Vario EL III. Melting
points were measured in capillaries sealed under argon and are
uncorrected.
Hydrido(2-diphenylphosphino)thiophenolato-[P,S]-bis(trimeth-
ylphosphine)nickel(II) (1). To the solution of tetrakis(trimeth-
ylphosphine)nickel(0) (1.30 g, 3.60 mmol) in 80 mL of pentane
was added 2-diphenylphosphinothiophenole (1.05 g, 3.60 mmol)
in the presence of excess trimethylphosphine (1.80 g, 18.4 mmol).
After stirring at room temperature for 16 h the reaction solution
1
1547 (CdC) cm-1. H NMR (300 MHz, C6D6, 294 K, ppm): δ
(SiCH3), 0.20 (s, 9H); δ (PCH3), 1.33 (d, 2J(PH) ) 8.7 Hz, 9H); δ
(Ni-C-CH2), 5.78 (s, 1H), 6.13 (s, 1H); δ (CHarom), 6.78-8.34 (m,
14H). 13C NMR (75 MHz, C6D6, 297 K, ppm): δ (SiCH3), 1.0; δ
(PCH3), 15.0 (d, 1J(PC) ) 27 Hz); δ (Ni-C-CH2), 121.3 (d, 3J(PC)
2
2
) 5 Hz); δ (Ni-C-CH2), 159 (dd, J(PC) ) 16 Hz, J(PC) ) 38
Hz); δ (Carom), 128.3, 129.4, 129.9, 130.7, 132.0, 132.3, 133.9,
135.5. 31P NMR (121 MHz, C6D6, 295 K, ppm): δ (PCH3), -14.2
(d, 2J(PP) ) 280 Hz, 1P); δ (PPh2), 46.8 (d, 2J(PP) ) 280 Hz, 1P).
(17) Liu, S. H.; Xia, H. P.; Wen, T. B.; Zhou, Z.; Jia, G. Organometallics
2003, 22, 737.
(18) Klein, H.-F.; Karsch, H. H. Chem. Ber. 1976, 109, 2515.
(19) Block, E.; Ofori-Okai, G.; Zubieta, J. J. Am. Chem. Soc. 1989, 111,
2327.
[(1-n-Butylethenyl)[(2-diphenylphosphino)thiophenyl(S,P)]-
trimethylphosphine]nickel(II) (6). Tetrakis(trimethylphosphine)-
nickel(0) (1.07 g, 2.95 mmol) was dissolved in 30 mL of THF. To
this solution was added 2-(diphenylphosphino)benzenethiol (0.86
g, 2.92mmol) in 20 mL of THF at -80 °C. The mixture was stirred
and immediately turned to dark red when it was warmed to 20 °C.
1-Hexyne (0.24 g, 2.92mmol) was injected into the above mixture.
After 18 h, the reaction solution turned to brown. After filtration
(20) Hessler, J. C. J. Am. Chem. Soc. 1922, 44, 425.
(21) (a) Brandsma, L. PreparatiVe Acetylenic Chemistry, 2nd ed.;
Elsevier: New York, 1988; p 114. (b) Organic Synthesis; John Wiley and
Sons: New York, 1963; Collect. Vol. IV.
(22) Walton, D. R. M.; Waugh, F. J. Organomet. Chem. 1972, 37, 45.
(23) (a) Tour, J. M.; Rawlett, A. M.; Kozake, M.; Yao, Y.; Jagessar, R.
C.; Dirk, S. M.; Price, D. W.; Reed, M. A.; Zhou, C.-W.; Chen, J.; Wang,
W.; Campbell, I. Chem.-Eur. J. 2001, 7, 5118. (b) Kang, S.-K.; Ryu, H.-
C.; Hong, Y.-T. J. Chem. Soc., Perkin Trans. 1 2001, 7, 736.

570 Organometallics, Vol. 26, No. 3, 2007
She et al.
and evaporation of the filtrate under vacuum, 70 mL of pentane
was employed to dissolve the residue. The filtrate was cooled at
-27 °C, and orange crystals were obtained. Yield: 0.96 g (64%),
mp (dec) > 97.5 °C. Anal. Calcd for C27H34NiP2S (511.27 g/mol):
C, 63.43; H, 6.70. Found: C, 63.71; H, 6.96. IR (Nujol): ν ) 1569,
was extracted with pentane/diethyl ether. From the pentane extract
at -20 °C complex 8 was obtained as yellow-brown microcrystals.
Yield: 0.34 g (30%), mp (dec) > 130 °C. Anal. Calcd for C52H54-
Ni2P4S2 (984.38 g/mol): C, 63.45; H, 5.53. Found: C, 63.67; H,
1
5.38. IR (Nujol): ν ) 1567, 1544 (CdC) cm-1. H NMR (300
1
2
1548 (CdC) cm-1. H NMR (300 MHz, CDCl3, 296 K, ppm): δ
MHz, C6D6, 294 K, ppm): δ (PCH3), 1.09 (d, J(PH) ) 7.8 Hz,
2
[P (CH3)3], 1.41 (d, J(PH) ) 8.7 Hz, 9H); δ (C-CH2-CH2), 1.75
18H); δ (Ni-C-CH2), 5.11 (s, 2H), 6.03 (s, 2H); δ (CHarom), 6.66-
(m, 2H); δ (C-CH2-CH2-CH2), 0.91 (m, 4H); δ (CH2-CH3), 0.62
(m, 3H); δ (CdCH2), 4.50 (s, 1H), 5.07 (s, 1H); δ (CHarom), 6.80-
8.06 (m, 14H). 13C NMR (75 MHz, CDCl3, 298 K, ppm): δ
8.02 (m, 32H). 13C NMR (75 MHz, C6D6, 298 K, ppm): δ (PCH3),
1
13.69 (t, | J(PC) + 3J(PC)| ) 50 Hz); δ (Ni-C-CH2), 111.9; δ (Ni-
C-CH2), 164.4 s; δ (C-S), 158.9; δ (CH2-C-C), 146.7; δ (Carom),
119.3, 125.2, 126.7, 132.0, 135.0, 135.8, 136.5, 137.2. 31P NMR
(121 MHz, C6D6, 295 K, ppm): δ (PCH3) -13.2 (d, 2J(PP) ) 280
1
3
[P(CH3)3], 13.82 (t, | J(PC) + J(PC)| ) 59 Hz); δ (CH2-CH3),
23.64; δ (C-CH2-CH2-CH2), 30.76; δ (C-CH2-CH2), 39.16; δ (Cd
CH2),114.0; δ (CdCH2), 160.3; δ (Carom), 121.6, 130.0, 130.9,
132.0, 133.7, 136.3, 137.1. 31P NMR (121 MHz, CDCl3, 296 K,
ppm): δ [P(CH3)3], -12.8 (d, 2J(PP) ) 278 Hz, 1P); δ (PhPPh2),
2
Hz, 2P); δ (Ph-PPh2), 51.5 (d, J(PP) ) 280 Hz, 2P).
Crystallographic Data for 3. C29H30NiP2S, Mr ) 531.2, crystal
dimensions 0.24 × 0.22 × 0.20 mm, monoclinic, space group P2-
(1)/c, a ) 18.930(4) Å, b ) 9.722(2) Å, c ) 15.502(3) Å, â )
105.691(4)°, V ) 2746.6(10) Å3, T ) 294(2) K, Z ) 4, Dc ) 1.285
g cm-3, µ ) 0.914 mm-1. Bruker AXS SMART APEX. A total of
14 953 reflections were collected, 5688 unique (Rint ) 0.0860), θmax
) 26.59°, multiscan absorption correction. R1 ) 0.0643 (for 5688
reflections with I > 2σ(I)), wR2 ) 0.1860 (all data). The structure
was solved by direct methods and refined with full-matrix least-
squares on all F2 (SHELXL-97) with non-hydrogen atoms aniso-
tropic.
2
50.8 (d, J(PP) ) 278 Hz, 1P).
[(Z,E)-(1-(4-(trimethylsilylethenyl)phenyl)-2-(trimethylsilyl)-
ethenyl)[(2-diphenylphosphino)thiophenyl(S,P)]trimethylphos-
phine]nickel(II) (7). Tetrakis(trimethylphosphine)nickel(0) (0.96
g, 2.64 mmol), 2-(diphenylphosphino)benzenethiol (0.77 g, 2.62
mmol), and 1,4-bis(timethylsilylethynyl)benzene (0.71 g, 2.63
mmol) were each dissolved in 25 mL of diethyl ether. To tetrakis-
(trimethylphosphine)nickel(0) was added 2-(diphenylphosphino)-
benzenethiol at -80 °C, giving a dark red suspension at ca. 20 °C.
Addition of 1,4-bis(timethylsilylethynyl)benzene to this solution
formed a brown suspension. After 18 h diethyl ether was removed
in vacuo, and the residue was extracted with pentane/diethyl ether.
From the pentane extract at -27 °C complex 7 was isolated as a
yellow powder. Yield: 1.38 g (76%), mp (dec) > 120 °C. Anal.
Calcd for C31H42NiP2SSi2 (623.53 g/mol): C, 59.72; H, 6.79.
Found: C, 60.10; H, 6.95. IR (Nujol): ν ) 2153 (CtC); 1597,
Crystallographic Data for 5. C26H34NiP2SSi, Mr )527.3, crystal
dimensions 0.20 × 0.16 × 0.14 mm, triclinic, space group P1h, a
) 10.589(2) Å, b ) 11.128(2) Å, c ) 12.139(2) Å, R ) 104.4(3)°,
â ) 104.69(3)°, γ ) 90.20(3)°, V ) 1336.7(5) Å3, T ) 273(2) K,
Z ) 2, Dc ) 1.310 g cm-3, µ ) 0.980 mm-1. A total of 7761
reflections were collected, 5223 unique (Rint )0.0678), θmax
)
27.10°, semiempirical absorption correction. R1 ) 0.0437 (for 5223
reflections with I > 2σ(I)), wR2 ) 0.1183 (all data). The structure
was solved by direct methods and refined with full-matrix least-
squares on all F2 (SHELXL-97) with non-hydrogen atoms aniso-
tropic.
1
1569, 1524 (CdC) cm-1. H NMR (300 MHz, CDCl3, 294 K,
ppm): δ (SiCH3), -0.158 (s, 9H), 0.230 (s, 9H); δ (PCH3), 1.48
2
(d, J(PH) ) 8.4 Hz, 9H); δ (Ni-C-CH), 6.78 (s, 1H); δ (CHarom),
6.81-8.18 (m, 18H). 13C NMR (75 MHz, CDCl3, 296 K, ppm): δ
(SiCH3), -0.34, 1.77; δ (PCH3), 15.3 (d, 1J(PC) ) 26 Hz); δ (Ni-
CCDC-614951 (3) and CCDC-614952 (5) contain the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge on application to CCDC, 12 Union Road,
Cambridge CB21EZ, UK (fax: (+44)1223-336-033; e-mail:
deposit@ccdc.cam.ac.uk).
3
3
C-CH), 141.7 (dd, J(PC) ) 23 Hz, J(PC) ) 7.5 Hz); δ (Ni-C-
CH), 157.0; δ (Ph-CtC), 105.7; δ (Ph-CtC), 93.6; δ (CHarom),
126.6, 128.0, 128.4, 129.4, 130.3, 130.7, 131.4, 132.0, 133.4, 133.8.
31P NMR (121 MHz, CDCl3, 295 K, ppm): δ (PCH3)(E), -14.5
(d, 2J(PP) ) 345 Hz, 0.19P); δ (PCH3)(Z), -12.9 (d, 2J(PP) ) 280
Hz, 0.81P); δ (PPh2)(E), 49.0 (d, 2J(PP) ) 345 Hz, 0.19P); δ
Acknowledgment. We gratefully acknowledge support by
NSF China Nos. 20572062 and 20372042 and The Doctoral
Program of Ministry of Education of China (MOE) Nos.
20050422010 and 20050422011.
2
(PPh2)(Z), 47.1 (d, J(PP) ) 280 Hz, 0.81P).
[Ni(2-PPh2C6H4S)(S,P)(PMe3)]2(µ-C(dCH2)-p-C6H4-C(dC-
H2)-) (8). Addition of 2-(diphenylphosphino)benzenethiol (0.66
g, 2.24 mmol, in 20 mL of THF) to tetrakis(trimethylphosphine)-
nickel(0) (0.82 g, 2.26 mmol, in 40 mL of THF) immediately
afforded a dark red solution. 1,4-Bis(ethynyl)benzene (0.14 g, 1.11
mmol, in 20 mL of THF) was added to the above solution, and the
mixture was stirred 18 h at room temperature. A yellow-brown
solution was obtained. After evaporating the volatiles, the residue
Supporting Information Available: Tables containing full
X-ray crystallographic data for 3 and 5. These materials are
available free of charge via the Internet at http://pubs.acs.org.
OM0606340